Water insoluble azodyestuff and fiber dyed therewith



Patented Aug. 8, 1933 TWATERSINSOLUBLE AZODYESTUFF AND FIBER DYED'rnnnnwrrn Leopold Laska and Arthur Zitscher, Offenbachon-the-Main',Germany, assignors to General Aniline Works, Inc, New

ration of Delaware York, N. Y., a Corpo- No Drawing. Application ram 221929, Serial No. 387,793, and in Germany August 25,- 1928 2-": Claims.(erase-s4 Our present invention relates to new waterinsolubleazodyestuffs and to fiber dyed there.- with; more particularly itrelates to az'odyestuifs corresponding probably to the general formula:

wherein one X mea'ns hydrogen and the other a methoxy-group, one Ystands for hydrogen and the other Y for hydrogen; alkyl, alkoxy orhalogen, Z stands for hydrogen, the residue N=Naryl or the residue a1k10C -HN-00 wherein X and Y have the above indicated meaning and arylrepresents the residue of an aromatic diazotizable amino compoundnotcontaining any groups, such as the sulfonic acid or the carboxylic acidgroup, which would render the dyestufis soluble in Water or alkalies.The new compounds are obtainable bycombining in substance or. on asubstratum, particularly on thefiber any diazo-, tetrazoordiazoazo-compound not containing any groups, such as the sulfonic acidor the carboxylic acid group, which would render the dyestuffs solublein water or alkalies, with a 2.3-hydroxynaphthoyli-aminobenZene-compoundof the general formula:

wherein the Xs and Ys ha've the aforesaid signification. The newdyestuffs may be used for the production of valuable color lakes; when'produced on the fiberthey yield fast dyeings and printings.Cornpared'with the known dyestuffs derived from2.3-hydroXy-naphthoyl-4-amino-1r' of thearylide residue'increases the:fastness ,to light to such an extent that even when simple and cheapdiazocomponents', such as for example meta-xylidine, are used dyestuffsof a remarkably good fastness to light are obtained.v By theintroduction of yet another substituent (alkyl,

- alkoxy, halogen) into the arylide residuethe fastness to light is insome cases further improved. The dyeings thus obtainable can'be renderedstill more fast to light by anaftertreatment with 5 metallic salts,suc'hfas', for instance, copper salts. In order to further illustrateour invention, the

following examples are given, the parts being by v Example 1 16.8 parts'off4-nitro-2-anisidine are diazotized in the usual manner and thediazocompound is combined ,With ajsolution of .34 parts of 2.3hy

d'roxynaphthoyl-el-amino-l;3 dime thoxybenzene in a dilute'caustic sodasolution containing Turkey red oil and an amount of sodium acetate suf-S0 ficient for binding the excess of the mineral acid. The separateddyestuff isfiltered off'and'washed. Mixed with'thefusu'al substrata ityields bluish red color lakes of a very good fastness to light.

' Example 2 Cotton material previously treated in the usual manner isimpregnated with-a solution containing dgrs. of2.3-hydroxynaphthoyl-4amino-1.3 dimethoxybenzene, 9 ccm/of-a causticsoda solution of. 34-B$ and 9 com. of Turkey red oil in the liter, anddeveloped, after havingbeen squeezed off, with a diazo-solutioncontaining 1.62 grs. of 2.4-dichloroaniline the liter and having beenneutralized with sodium acetate. The material is then Worked upas usual.In this manner yellowishred dyeings of a ver good fastness tolight areobtained. v 7

When

2.3 hydroxynaphthoyl-i-amino-3 methoxy-l-ethoxy -benzene is used insteadof- 2.? 1hydroxynaphthoyl-e-amino 1.3 -dimethoxy benzene dyeings Cponding properties are obtained. r

- Example 3 Cotton material previously'treated in' 'the' usual manner isimpregnated with a solution containing 10 grs. of2.3-hydroxynaphthoyl-4-amino 1.2- dimethoxybenzene, 15 com. of a causticsoda solution of 34 B.,and '20 com. of Turkey red oil in the liter, anddeveloped, after having been 10 Flee l 5-nitro-2-anisid1ne.-..

- l-arnino-anthraquinone squeezed off, with a diazosolution containing1.62 grs. of 2.5 dichloro-aniline in the liter and having beenneutralized with sodium acetate. The material is then worked up asusual.

In this manner a brownish red dyeing of a very good fastness to light isobtained.

A brownish orange dyeing of a still better fast- Diazocompound of Shadeobtained m-xylidine Red 4-chloro-2-tolu Red B-chloro-Z-toluidin Full red.S-nitro-aniline Brownish red '4-nitr0-2-toluid Clear red5-nitro-2-anisidine Bluish claret 4-amino-3.2 -dimet arnet dianisidine(subsequently treated with Reddish dark blue Yellowish red R d perm-chloroaniline. 6-chloro-2toluidin o-nit-roaniline 4-chloro-2-nitroani2chloro-4-nitroaniline. 3-nitro-4-t0luidine 5-nitro-2-toluidinel-aminoanthra quinone Brownish red Idem Idem Red

Claret Copper brown derived from 2.3-hydroXynaphthoyl-4-amino-6-chloro-1.3 -dirnethoxy -benzene:

Diazocompound of Shade obtained '4-chloro-2-toluidine Red5-chloro-2-toluidine Bluish red 6-chloro-2-to1uidine Yellowish redZ-amin'o-4-chloro-diphenylether. Claret 2-arnino-5-chloro-diphenyletherBluish red 3-nitroalinine Yellowish red 4-nitro-2-toluidine Clear red4-nitro-2-anisidine. Clear red l-aminoanthraquinone Claret brown2-phenet0l-azo-u-naphthylarnine Black 2.5-dichlo'roanilineL Brick-redzA-dichloroanilinea Red 3-nitro-4-t0luidinc Yellowish red 4-amino-3.2dimethyl-Ll azo-benzene Bluish garnet derived from2.3-hydroxynaphthoyl-4-amino-6- methyl-LB-diniethOXy-benZene':

Diazocompound of Shade obtained m-x ylidine .l Clear bluish red2.5dichloroaniline Orange brown fi-chloroQ-toluidine-.. Bluish red2.4.S-trichloro-aniline.

Z-nitro-aniline 4-chlor0-5-bromo-2-t01uidine 3-nitro-4-toluidineBrownish red Red like claret Dark bluish red Red like claret Dark bluishred like claret Bluish garnet 4-amino-3.2 dimethyl-Ll azo-benzeneBrownish red derived from 2.3 hydroxynaphthoyl 4. amino-1.3.fi-trimethoxy-benzenez Diazocompound of Shade obtained Red likeclaret Brownish red Red Bluish garnet Brownish red Black5-chloro-2-toluidine' 4-nitro-2-toluidine 4-nitro-2-anisidin4-arnino-3.2 dimet 1-aminoanthraquinone 4-nitro-2.5-dimethoxy-4-aderived from 2.3-hydroxynaphthoyl-4-arnino-1.2- dirnethoxybenzeneDiazocompound of Shade obtained 3-chloroaniline Copper4-nitro-2-toluidine... Yellowish red 4-nitro-2-anisidine Yellowish redl-amino-3.2 dimethyl-Ll azo-benzene Bluish garnet2-phenetol-azo-a-naphthylamine Black 4-chloro-2-anisidine Claret5-ch10ro-2-to1uidine 2-chloro-4-nitroauiline Red brown3-nitro-4-toluidine Brownish red 5-nitro-2-toluidine Ideml-aminoanthraquinone Idem derived from 2.3 hydroxynaphthoyl-4-am1no-5chloro- 1.2 dirnetnoxybenzene Diazocompound of Shade obtained4-nitro-2-toluidine Covered red G-chloro-Z-toluidine. Covered redZ-nitroaniline. Brown 4-nitroaniline. Red-brown 5-nitro-2-toluidineRed-brown 4-nitro-2-anisidine Dark red 5nitro-2-anisidine Brown garnetZ-chloro-i-nitroaniline Brown 4-chloro-2-toluidine. Bluish red 74-nitr0-2-toluidine. Red tarmac-3.2 dirnethyl-1.l azobenzene GarnetZ-phenetol-azo-a-napthylamine Blue black Since an object of the presentinvention is to provide dyestuffs of good fastne'ss properties, whichdyestuffs are insoluble in water and alkalies, it is to be understoodthat the aromatic nuclei of the general formulae appearing in theappended claims contain no substituentsas are known to render organiccompounds soluble in water or alkalies and to tend to depreciate thefastness of the dyestufis to alkalies. Substituents of this kind-are thesulfonic acid, the carboxylic acid and the hydroxy group.

We claim:

1. As new compounds, the water-insoluble azodyestuffs correspondingprobably to the general wherein one X and one Y mean hydrogen, the otherX a methoxy group, the other Y hydrogen, halogen, an alkyl or alkoxygroup wherein Z stands for hydrogen, an aryl diazo radical of thebenzene series or theresidue usual substrate. valuable orange to red toblue to black'coior lakes and orange to red to blue'to black dyeingsfast to light when produced on the fiber.

2. As new compounds, the water-insoluble azodyestuffs correspondingprobably to the general formula:

wherein one X and oneY mean hydrogen, the

other X a methoxy-group, the other -Y hydrogen,

halogen, an alkyl or alkoxy-group, and wherein Z stands for hydrogen oran 'aryldiazo radical of the benzene series, which. dyestuffs yield whenmixed with the usual substrata valuable orange to red to blue to blackcolor lakes and orange to red to blue to black dyeings fast to lightwhen produced on the fiber. Y

3. As'new compounds, the water-insoluble azodyestuffs correspondingprobably to the general formula:

wherein one X andone Y mean hydrogen, the other X a methoXy-group, theother Y hydrogen, halogen, an alkyl' or alkoxy-group and wherein Rstands for a radical of the benzene series, which dyestuffs yield whenmixed with the usualsubstrata valuable red to blue to black color lakesand red to blue to black dyeings fast to light when produced on'thefiber.

4. As new compounds, the water-insoluble azodyestuffs correspondingprobably to the general formula:

o'oamG-o I 0113' I OOHs wherein one Y means hydrogen, the other Yhydrogen, halogen, an akyl 0r alkoxy-group and wherein R stands for aradical of the'benzene series, which dyestuffs yield when mixed with theusual substrata valuable red to blue to black c0101 lakes and red toblue to black dyeings fast to light when produced on the fiber...

5. As new compounds, the water-insoluble azodyestuffs correspondingprobably to the general formula:

wherein one Y means hydrogen the other Y hydrogen, halogen, an alkyloralkoxy-group, which dyestuffs yield when mixed with the usual substratavaluable orange to red to blue to black color lakes and orange to red toblue toblack dyeings fast to light when produced on the fiber.

6.'As new compounds, thewater-insoluble azo dyestuffs correspondingprobably to the general formula;

O CHa wherein R stands for a radical of the benzene series, whichdyestuffs yield when mixed with the usual substrata valuable red to blueto black color lakes and red to blue to black dyeings fast to light whenproduced onthe fiber. V p

'7. As new compounds, the water-insoluble azodyestuffs correspondingprobably to the general formula: 7 i

'OOHa which dyestuffs yield when mixed withthe usual 1 substratavaluable orange to red to blue color lakes and orange to red. to bluedyeings fast to light when produced on the fiber.

9. As a new compound, the water-insoluble azodyestuff correspondingprobably tothe following 5 formula: 1 r

N= CH3 7 OCH3 CO-NH OCHa which dyestuff yields valuable red dyeings fastto light when produced on the fiber.

10. As a new compound, the water-insoluble azodyestufi correspondingprobably to the following formula:

which dyestuffyields valuable'bluish claret dyeings fast to light whenproduced on the fiber.

11. As a new compound, the water-insoluble azodyestuff correspondingprobably to the followv (IX-1H3 which dyestufi yields valuableblackdyeings fast to light when produced on the fiber.

' 12. Fiber dyed with the azodyestuffs as claimed in claim 1. V

13. Fiber dyed with the azodyestuffs as claimed in claim 2.

14. Fiber dyed with the azodyestuffs as claimed in claim 3.

15. Fiber dyed with the azodyestuffs as claimed in claim 4.

16. Fiber dyed with the azodyestuffs as claimed in claim 5.

1'7. Fiber dyed with the azodyestuffs as claimed in claim 6. y

18. Fiber dyed with the azodyestufis as claimed in claim '7.

19. Fiber dyed with the azodyestuffs as claimed in claim 8. I

20. Fiber dyed with the azodyestufi as claimed in claim 9.

21. Fiber dyed with the azodyestuff as claimed 4 in claim 10. c

22. Fiber'dyed with the azody'estuff as claimed in claim 11.

23. The method of making azodyestufis which comprises coupling anarylide of 2.3-hydroxynaphthoic acid having probably the formula 24. Anazo dyestuff having probably theformula wherein R represents an aromaticradical from a diazotized aromatic amino compound;

25. An azo dyestuff having probably the forwherein R represents anaromatic radical from a diazotized aromatic amino compound.

25. An azo dyestuff having probably the formula:

wherein R represents an aromatic radical from a diazotized aromaticamino compound.

' LEOPOLD LASKA.

ARTHUR ZITSCHER.

